We performed quasiresonant laser excitation of Li–Cd vapor mixtures at 460.3 nm (2p–4d) and 497.2 nm (2p–4s). The initial population of the Li(2p) level is caused by three processes: collisional dissociation or photodissociation of the Li2(B1Πu) molecules or energy transfer in Li2(B1Πu) and Li(2s) collisions. The Li(4d,4s) atoms radiatively decay towards Li(3p), from which collisional population transfer to Cd(53PJ) occurs, followed by three-body reactive collisions which produce the LiCd(22Π ) excimer states